Correlation of Thermoelectric Performance, Domain Morphology and Doping Level in PEDOT:PSS Thin Films Post-Treated with Ionic Liquids.

AbstractIonic liquid (IL) post‐treatment of poly(3,4‐ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) thin films with ethyl‐3‐methylimidazolium dicyanamide (EMIM DCA), allyl‐3‐methylimidazolium dicyanamide (AMIM DCA), and 1‐ethyl‐3‐methylimidazolium tetracyanoborate (EMIM TCB) is compared. Doping level modifications of PEDOT are characterized using UV–Vis spectroscopy and directly correlate with the observed Seebeck coefficient enhancement. With conductive atomic force microscopy (c‐AFM) the authors investigate changes in the topographic‐current features of the PEDOT:PSS thin film surface due to IL treatment. Grazing incidence small‐angle X‐ray scattering (GISAXS) demonstrates the morphological rearrangement towards an optimized PEDOT domain distribution upon IL post‐treatment, directly facilitating the interconductivity and causing an increased film conductivity. Based on these improvements in Seebeck coefficient and conductivity, the power factor is increased up to 236 µW m−1K−2. Subsequently, a model is developed indicating that ILs, which contain small, sterically unhindered ions with a strong localized charge, appear beneficial to boost the thermoelectric performance of post‐treated PEDOT:PSS films

Effect of Blend Composition and Additives on the Morphology of PCPDTBT:PC71BM Thin Films for Organic Photovoltaics.

The use of solvent additives in the fabrication of bulk heterojunction polymer:fullerene solar cells allows to boost efficiencies in several low bandgap polymeric systems. It is known that solvent additives tune the nanometer scale morphology of the bulk heterojunction. The full mechanism of efficiency improvement is, however, not completely understood. In this work, we investigate the influences of blend composition and the addition of 3 vol % 1,8-octanedithiol (ODT) as solvent additive on polymer crystallization and both, vertical and lateral morphologies of poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta [2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)] and [6,6]-phenyl C71-butyric acid methyl ester (PCPDTBT:PC71BM) blend thin films processed from chlorobenzene-based solutions. The nanoscale morphology is probed with grazing incidence small- and wide-angle X-ray scattering as well as X-ray reflectivity and complemented with UV/vis spectroscopy. In PCPDTBT:PC71BM films the use of ODT is found to lower the solubility of fullerene in the polymer matrix and to promote polymer crystallization, both vertical and lateral microphase separation with morphological coarsening, and formation of a fullerene-rich topping layer. The enhanced photovoltaic performance is explained by these findings

Ligand chemistry of inorganic lead halide perovskite nanocrystals

Lead halide perovskite nanocrystals (LHP NCs) have emerged as next-generation semiconductor materials with outstanding optical and optoelectronic properties. Because of the high surface-to-volume ratio, the optical and optoelectronic performance and the colloidal stability of LHP NCs largely depend on their surface chemistry, especially the ligands and surface termination. On one hand, the capping ligands improve the colloidal stability and luminescence; on the other hand the highly dynamic binding nature of ligands is detrimental to the colloidal stability and photoluminescence of LHP NCs. In addition, the surface functionalization with desired molecules induces new functionalities such as chirality, light harvesting, and triplet sensitization through energy/electron transfer or use as X-ray detectors. In this review, we present the current understanding of an atomic view of the surface chemistry of colloidal LHP NCs, including crystal termination, vacancies, and different types of capping ligands. Furthermore, we discuss the ligand-induced functionalities, including photocatalysis and chirality.Deutsche Forschungsgemeinschaft | Ref. EXC 2089/1 390776260Xunta de Galicia | Ref. ED431F2021/05Agencia Estatal de Investigación | Ref. RYC2018-026103-IAgencia Estatal de Investigación | Ref. PID2020-117371RA-I00Universidade de Vigo/CISU

Electronic properties of hybrid organic/inorganic semiconductor pn-junctions

Hybrid inorganic/organic semiconductor heterojunctions are candidates to expand the scope of purely organic or inorganic junctions in electronic and optoelectronic devices. Comprehensive understanding of bulk and interface doping on the junction’s electronic properties is therefore desirable. In this work, we elucidate the energy level alignment and its mechanisms at a prototypical hybrid pn-junction comprising ZnO (n-type) and p-doped N,N′-di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (α-NPD) as semiconductors, using photoelectron spectroscopy. The level alignment can be quantitatively described by the interplay of contact-induced band and energy level bending in the inorganic and organic component away from the interface, and an interface dipole due to the push-back effect. By adjusting the dopant concentration in α-NPD, the position of the frontier energy levels of ZnO can be varied by over 0.5 eV and that of α-NPD by over 1 eV. The tunability of this pn-junction’s energy levels evidences the substantial potential of the hybrid approach for enhancing device functionality.Deutsche Forschungsgemeinschafthttps://doi.org/10.13039/501100001659Peer Reviewe

Increasing Photostability of Inverted Nonfullerene Organic Solar Cells by using Fullerene Derivative Additives

Organic solar cells (OSCs) recently achieved efficiencies of over 18% and are well on their way to practical applications, but still considerable stability issues need to be overcome. One major problem emerges from the electron transport material zinc oxide (ZnO), which is mainly used in the inverted device architecture and decomposes many high-performance nonfullerene acceptors due to its photocatalytic activity. In this work, we add three different fullerene derivatives—PC71BM, ICMA, and BisPCBM—to an inverted binary PBDB-TF:IT-4F system in order to suppress the photocatalytic degradation of IT-4F on ZnO via the radical scavenging abilities of the fullerenes. We demonstrate that the addition of 5% fullerene not only increases the performance of the binary PBDB-TF:IT-4F system but also significantly improves the device lifetime under UV illumination in an inert atmosphere. While the binary devices lose 20% of their initial efficiency after only 3 h, this time is increased fivefold for the most promising ternary devices with ICMA. We attribute this improvement to a reduced photocatalytic decomposition of IT-4F in the ternary system, which results in a decreased recombination. We propose that the added fullerenes protect the IT-4F by acting as a sacrificial reagent, thereby suppressing the trap state formation. Furthermore, we show that the protective effect of the most promising fullerene ICMA is transferable to two other binary systems PBDB-TF:BTP-4F and PTB7-Th:IT-4F. Importantly, this effect can also increase the air stability of PBDB-TF:IT-4F. This work demonstrates that the addition of fullerene derivatives is a transferable and straightforward strategy to improve the stability of OSCs

Lithium distribution and transfer in high-power 18650-type Li-ion cells at multiple length scales

The distribution of lithium inside electrodes of a commercial Li-ion battery of 18650-type with LiFePO$_{4}$ cathode and graphite anode is investigated on different length scales using neutron diffraction, X-ray (synchrotron-based) diffraction and X-ray computed tomography. Evolution of 2D (in-plane) lithium distribution in lithiated graphite is monitored during charge/discharge using millimeter-sized spatial resolution. Micrometer-sized details of cell organization and lithiation of both the positive and negative electrodes are obtained from diffraction-based tomography applying synchrotron radiation. In-situ lithiation of the cathode over its thickness and development of the lithium concentration front during cell charge/discharge is traced by diffraction-based profiling with a micrometer-sized synchrotron beam in a single-layer electrochemical cell

Self-Assembly of Polymer-Modified FePt Magnetic Nanoparticles and Block Copolymers

The fabrication of nanocomposites containing magnetic nanoparticles is gaining interest as a model for application in small electronic devices. The self-assembly of block copolymers (BCPs) makes these materials ideal for use as a soft matrix to support the structural ordering of the nanoparticles. In this work, a high-molecular-weight polystyrene-b-poly(methyl methacrylate) block copolymer (PS-b-PMMA) was synthesized through anionic polymerization. The influence of the addition of different ratios of PMMA-coated FePt nanoparticles (NPs) on the self-assembled morphology was investigated using transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). The self-assembly of the NPs inside the PMMA phase at low particle concentrations was analyzed statistically, and the negative effect of higher particle ratios on the lamellar BCP morphology became visible. The placement of the NPs inside the PMMA phase was also compared to theoretical descriptions. The magnetic addressability of the FePt nanoparticles inside the nanocomposite films was finally analyzed using bimodal magnetic force microscopy and proved the magnetic nature of the nanoparticles inside the microphase-separated BCP films

Layer-by-Layer Spray-Coating of Cellulose Nanofibrils and Silver Nanoparticles for Hydrophilic Interfaces

Silver nanoparticles (AgNPs) and AgNP-based composite materials have attracted growing interest due to their structure-dependent optical, electrical, catalytic, and stimuli-responsive properties. For practical applications, polymeric materials are often combined with AgNPs to provide flexibility and offer a scaffold for homogenous distribution of the AgNPs. However, the control over the assembly process of AgNPs on polymeric substrates remains a big challenge. Herein, we report the fabrication of AgNP/cellulose nanofibril (CNF) thin films via layer-by-layer (LBL) spray-coating. The morphology and self-assembly of AgNPs with increasing number of spray cycles are characterized by atomic force microscopy (AFM), grazing-incidence small-angle X-ray scattering (GISAXS), and grazing-incidence wide-angle X-ray scattering (GIWAXS). We deduce that an individual AgNP (radius = 15 ± 3 nm) is composed of multiple nanocrystallites (diameter = 2.4 ± 0.9 nm). Our results suggest that AgNPs are assembled into large agglomerates on SiO2 substrates during spray-coating, which is disadvantageous for AgNP functionalization. However, the incorporation of CNF substrates contributes to a more uniform distribution of AgNP agglomerates and individual AgNPs by its network structure and by absorbing the partially dissolved AgNP agglomerates. Furthermore, we demonstrate that the spray-coating of the AgNP/CNF mixture results in similar topography and agglomeration patterns of AgNPs compared to depositing AgNPs onto a precoated CNF thin film. Contact-angle measurements and UV/vis spectroscopy suggest that the deposition of AgNPs onto or within CNFs could increase the hydrophilicity of AgNP-containing surfaces and the localized surface plasmon resonance (LSPR) intensity of AgNP compared to AgNPs sprayed on SiO2 substrates, suggesting their potential applications in antifouling coatings or label-free biosensors. Thereby, our approach provides a platform for a facile and scalable production of AgNP/CNF films with a low agglomeration rate by two different methods as follows: (1) multistep layer-by-layer (LBL) spray-coating and (2) direct spray-coating of the AgNP/CNF mixture. We also demonstrate the ability of CNFs as a flexible framework for directing the uniform assembly of AgNPs with tailorable wettability and plasmonic properties

Attitude Determination in Space with Ambient Light Sensors using Machine Learning for Solar Cell Characterization

Exploration of novel thin-film solar cell technologies outreaches for their application in space. For extraterrestrial tests, irradiance conditions must be well determined to extract quantitative solar cell performances. Here, a new method for solar position determination is presented, based on parallelized ambient light sensor measurements is presented obtained from the sounding rocket experiment Organic and Hybrid Solar Cells In Space during the MAPHEUS-8 mission. The solar position evolution is optimized using stochastic and gradient-based methods in a Bayesian approach. Comparison with independent positioning estimates shows compelling agreement, lying mostly within 5° deviation. The inclusion of a simple Earth irradiation component mitigates a small systematic offset. Further, solution uncertainties are estimated with Monte-Carlo Markov-chain sampling. The point-source irradiation model's accuracy can compete with that of a camera-based trajectory. During equatorial Sun positions, the method's precision appears even higher––the 1σ uncertainty of the derived solar position is as small as 3° for the effective angular deviation. This simple sensor array triangulation method being complementary to other attitude determination methods shows reasonable accuracies and allows implementation in systems of limited computational capabilities to determine the solar position or irradiance conditions for space or terrestrial solar cell applications

Self-Assembly of Polymer-Modified FePt Magnetic Nanoparticles and Block Copolymers

The fabrication of nanocomposites containing magnetic nanoparticles is gaining interest as a model for application in small electronic devices. The self-assembly of block copolymers (BCPs) makes these materials ideal for use as a soft matrix to support the structural ordering of the nanoparticles. In this work, a high-molecular-weight polystyrene-b-poly(methyl methacrylate) block copolymer (PSb-PMMA) was synthesized through anionic polymerization. The influence of the addition of different ratios of PMMA-coated FePt nanoparticles (NPs) on the self-assembled morphology was investigated using transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). The selfassembly of the NPs inside the PMMA phase at low particle concentrations was analyzed statistically, and the negative effect of higher particle ratios on the lamellar BCP morphology became visible. The placement of the NPs inside the PMMA phase was also compared to theoretical descriptions. The magnetic addressability of the FePt nanoparticles inside the nanocomposite films was finally analyzed using bimodal magnetic force microscopy and proved the magnetic nature of the nanoparticles inside the microphase-separated BCP films